TW200400201A - Nanoscale polymerized hydrocarbon particles and methods of making and using such particles - Google Patents

Abstract

This invention is cross-linked, polymerized hydrocarbon particles which composition is characterized in that the particles have an average diameter of less than 30 nm, the particles exhibit a volume swell factor of no greater than 3.0; the composition is essentially free of metal ions; the particles have a polydispersity (polystyrene relative Mw/Mn) of less than 3.0, and the particles are characterized by a Mark-Houwink plot having a slope with an absolute value of less than 0.4 for the peak molecular weight range. The invention is also a method of making nanoparticles having a weight average diameter less than 30 nm by emulsion polymerization in the substantial absence of ionic components. Finally, the invention is a method of using such particles as thermally degradable components in making porous films.

Description

200400201 发明, Description of invention:

[Technology of the Invention ^ I Field of the Invention The present invention was completed under the cooperation agreement No. 5 70NANB8H4013 awarded by NIST with the support of the federal government.

The present invention relates to high-purity nano-grade smoke particles, a method for manufacturing such particles using an emulsification technique, and a method for using such particles in the manufacture of nanoporous films. I [previously] 10 backgrounds

Very small, crosslinked, hydrocarbon-based polymer particles can be made by emulsion polymerization techniques. Although some techniques have been found to broadly describe any of the surfactants: anionic, cationic, or nonionic can be used, special teachings do not address the issue of particle size (for example, Donescu et 15 al., The Influence of Monomers upon Microemulsions with Short Chain Cosurfactant, J. Dispersion Sci. And Tech., Vol. 22, No. 2-3, 2001, pp. 231-244), or mention: "Nonionic surfactants alone in It tends to be ineffective when making very small particles "and" a small amount of anionic surfactant needs to be added to get the desired small particle size of 20 ". See, for example, TTze s

Resin Emulsions, H. Warson, Ernest Benn Ltd., 1972, p. 88 »and Larpent and Tadros, Preparation of Misrolatex Dispersions Using oil-in-Water Microemulsions, Colliod Polym. Sci. 269, 1171-1183 (1991). Capek et al. I / ze 200400201

Fine Emulsion Polymerization of Styrene With Non-Ionic 5 Polymer. Bull "43, 417-424 (1999) teaches that under the use of non-ionic polyoxyethylene sorbitan monolaurate, monoionic initiation The agent can help to obtain a small particle size (44-80 nm). 5 [Inside] Summary of the invention Compared to the teachings in this technology, the inventor of this case made a surprising discovery: extremely small particles (weight average diameter is less than 30%). Leg) can be obtained without any ionic additives using non-ionic surfactants and non-ionic starting agents. Therefore, according to a first specific example, the present invention is a composition comprising the following steps: Method: Combining at least one nonionic surfactant and at least one aqueous phase component, adding at least one monomer capable of performing radical polymerization 15 reaction, and adding-essentially selected from the group consisting of carbon, hydrogen, and oxygen A radical initiator composed of an atom of a nitrogen atom, and heating the plutonium to produce polymerized particles having a composition in which the composition is substantially free of ionicity at all

A surfactant having a weight average diameter of less than 30 nm in combination, addition, and heating steps, and substantially free of an initiator or initiator residue containing any atom other than carbon, hydrogen, oxygen, and nitrogen; and These addition and heating steps can occur in any order. Optionally, the method further comprises one or both of precipitating the particles and additional steps of purification to remove metals and / or ions. According to a specific example of the younger brother, the prefecture or Iksan + Zhiyueyan is a polymerized hydrocarbon particle prepared by the above method. 20 200400201 According to another specific example, the present invention is a composition comprising cross-linked polymerized hydrocarbon particles, the composition is characterized in that the particles have a weight average diameter of less than 30 nmi, and the particles exhibit With a volume expansion coefficient of not greater than, the particles are substantially free of metal ions; the 5 particles have a polydispersity (Mw / Mn) of less than 3.0, and preferably, the particles are characterized by a Mark-Houwink plot, which has a slope of absolute value less than 0.4 for the highest molecular weight range. According to yet another specific example, the present invention is the use of the crosslinked polymerized hydrocarbon particles for the manufacture of porous thermosetting films. 10. The so-called "polymerized hydrocarbon particles" refers to a polymer particle consisting essentially of carbon, hydrogen, oxygen, and nitrogen atoms. More preferably, the polymerized hydrocarbon particles are essentially composed of carbon, hydrogen, and oxygen. Atoms. The term "substantially free of ionic surfactants" means that no ionic surfactants are added to the polymerization reaction mixture, and any ionic surfactant that may be present as impurities such as 15 is Exist in quantities below 50 parts per million (by component weight). More preferably, the mixture is free of ionic surfactants. The so-called "starter that does not contain atoms other than carbon, hydrogen, oxygen, and nitrogen in the mass means that no such starter is added to the mixture, and this order exists as an impurity. The starter is present in an amount of less than 50 parts per million (based on the weight of the component). More preferably, the mixture does not contain atoms other than carbon, hydrogen, oxygen, and nitrogen The so-called "volume expansion coefficient" refers to the volume of the particle in a solvent divided by the volume of the particle when it is not expanded. The solvent is a non-crosslinked poly200400201 compound (based on the same monomer) It is a good solvent. A good solvent is one in which the strength of the polymer-solvent interaction is greater than the strength of the polymer-polymer interaction, and therefore the polymer chain in it is maximized. See also "Textbook of Polymer Science ,, FW 5 Billmeyer, Jr. 3rd. Ed., John Wiley & Sons, New York, 1984, p. 154. For polystyrene and many other hydrocarbon particles, tetrahydrofuran (the preferred solvent for Ding Xiong. As will be further outlined in the detailed description, the volume expansion coefficient can be conveniently measured by SEC / DV. By "substantially free of metal ions," it means that the particles contain, in groups of 10 trowels, any metal ion contamination that is less than 50 parts per million. More preferably, the particles contain less than Any metal ion of 2 ppm. The total metal ion content is preferably less than 10 ppm, more preferably less than 5 ppm, and most preferably less than 2 ppm. Brief description of the drawings 15 Figure 1 is related to the present invention A molecular weight distribution diagram of a sample of one of the representative particles and a Mark-Houwink diagram (inherent viscosity vs. molecular weight in log units). I [Embodiment 3 Detailed Description of Preferred Embodiments 20 It is a benefit as an effective way for silk to produce pure ion-free nano-grade polymerized hydrocarbon particles, because the ionic surfactants required by the conventional technical methods used to make such nano-sized particles and their related gold Removal of tartar is difficult and inefficient. If the surfactant is ionic, residues of ionic components (such as a gold 200400201 metal ion, sulfate, etc.) are either very difficult or difficult to remove. In addition, the teaching given in this technique is "It is difficult to reach a very small particle size without the presence of at least some ionic species", it is surprising that the use of all on Babe is The method of the fifth method of non-ionic surfactant species results in particles having a weight-average diameter of less than 30 nm. The non-ionic surfactant can be any kind that can emulsify a monomer mixture in water or other aqueous polymerization media. Nonionic surfactants are known, and it is preferred to microemulsify the monomer mixture and stabilize the resulting nanoparticle product in the aqueous phase. Examples of such nonionic surfactants include polyoxygen Ethylated Alkyl Phenol (Alkyl Phenol "Ethoxylate, or APE); Polyoxyethylated Linear Alcohol (Alcohol" Ethoxylate, or AE); Polyoxyethylated Secondary Alcohol, Polyoxyl Ethylene polypropylene glycol; Polyoxyethylated mercaptans; long-chain carboxylic acid esters; glycerol and polyglycerol esters composed of natural fatty acids; propylene glycol, sorbitol, and polyoxyethylated sorbitol esters; polyethylene glycol esters and polyoxyethylated fats 15 Acids; alkanolamine condensates; alkanolamines; alkyldiethanolamine, 1: 1 alkanolamine fatty acids, 2.1 alcohol amine-fatty acid condensates; tertiary acetylenic diols glyColls) (for example, R1R2C (〇H) c = c (〇H) RlR2); polyoxyethylated silicone; n-alkylpyrrolidone; polyoxyethylated 丨, 2-alkanediol and 1, 2-aryl alkanediol; and alkyl polysaccharides. Alkyl polyoxyethylene, poly 20 oxyethylated 1,2-alkanediol, and alkyl aryl polyoxyethylene compounds are preferred. Examples of commercially available nonionic surfactants include Tergitol ™ surfactant from The Dow Chemicals, and Triton ™ surfactant from The Dow Chemicals. The amount of surfactant used must be sufficient to at least substantially stabilize the nanoparticulate product that has been formed in water or other water -10- 200400201 5 10 15. The exact amount will vary depending on the selected surfactant and the entities of the other components. The application will also vary depending on whether the reaction is run as a batch reaction, a semi-batch reaction, or a continuous reaction. Batch reactions-generally require the highest amount of surfactant. In semi-batch reactions and continuous reactions, as particles grow and the surface area to volume ratio decreases, surfactants become available again, so less surfactant is needed to make and batch reactions. Of the same amount-particles of a given size. The applicant of this case has found ... "Surfactants

The weight of the monomer is 3: 1 to 1:20, and more preferably: to 1:15 ". The useful range may actually be wider than this. The aqueous phase component may be water or may be a combination of water and a hydrophilic solvent 'or-a hydrophilic solvent. The amount of the aqueous phase to be used, based on the total weight of the reaction mixture, is preferably at least 4 Gwt%, more preferably at least 5 Gwt%, and most preferably at least 6 Gwt%. The amount of the aqueous phase used is preferably not more than 99% by weight, more preferably not more than 95% by weight, still more preferably not more than 90%, and still more preferably not more than 85% by weight.

The initiator may be any radical initiator consisting essentially of carbon, hydrogen, oxygen and / or nitrogen, but more preferably consists essentially of carbon, hydrogen, oxygen. As used herein, "consisting essentially of" has the traditional meaning under U.S. Patent 20, that is, no component that would substantially alter the properties of a compound would exist in a substantially effective amount. Suitable initiators include, for example, 2,2, -azobis (2-methylfluorenylpropane) digas, and reducing oxidation initiators [such as H2O2 / ascorbic acid or butyl hydroperoxide / ascorbic acid] ], Or an oil-soluble starter [for example, di + butyl hydroperoxide, ^ butyl-11-200400201 peroxybenzoate or 2,2-azoisobutyronitrile]. The amount of the initiator to be added is preferably 0.01 to 5.0 parts by weight, more preferably 002 to 30 parts by weight, and most preferably 0.05 to 2.5 parts by weight (calculated based on the weight of the monomer of 100 parts by weight). ). The monomer is a monomer that can undergo radical polymerization. The monomers 5 are preferably compounds consisting essentially of only atoms selected from carbon, hydrogen, nitrogen and / or oxygen (more preferably remote from carbon, hydrogen and oxygen). Suitable monomers include those containing at least one unsaturated carbon-carbon bond. A single type of monomer may be used or different monomers may be used together. Examples of monomers having an unsaturated carbon-carbon bond that can be used in the reaction include styrene (e.g., stilbene-10ene, alkyl substituted with styrene, aryl substituted with phenyl ethyl, fast aryl Alkyl-substituted acetophenone and the like); Acrylic acid and methyl acrylic acid (such as' Arythyl acrylate or Arythyl methyl acrylic acid and the like); Ethylene Substrates (such as vinyl acetate, alkyl vinyl ether, and the like); allyl compounds (such as allyl acrylate); olefins (such as 15 butene, hexene, heptene, etc.). Examples of monomers having more than one unsaturated carbon-carbon bond that can be used for the reaction include alkadiene (eg, butadiene, isoprene); divinylbenzene or 1,3-diisoprene Benzene; alkylene glycol diacrylate and the like. According to a preferred embodiment, the polyhydrocarbon particles are crosslinked. In a preferred embodiment of this -0, at least a part of the monomer has more than one unsaturated carbon-carbon bond. The use of a styrene monomer system having divinylbenzene or 1,3-diisoprenylbenzene is a particularly preferred example. When used, the amount of cross-linking monomer used (ie, a monomer having more than one carbon-carbon bond available for reaction), preferably based on the total weight of the monomer, is less At about 200,400,201 100 Wt%, more preferably less than 70 wt%, most preferably less than 50 wt%, and more preferably a large Wwm, more preferably. The total amount of monomers added to the composition is from 1 to palpitate, based on the total weight of the composition, preferably from 3 to 45 wt%, more preferably from 5 to 35 wt%. Alternatively, an additional lipophilic solvent may be added to the monomer. Non-limiting examples of suitable solvents include benzene, ethylbenzene, 3,5-triphenylene), cyclohexane, hexane, dibenzene, octane, and the like, and combinations thereof. If used, the amount of the lipophilic solvent, based on the weight of the lipophilic phase, may be 1 to 9-%, preferably 2 to 7_%, and most preferably 10 to 5 to 50 Wt%. The total amount of lipophilic phases must be that of all the mixtures! Up to 60 /. 'Is preferably from 3 to 45%, more preferably from 5 to 35/0. The process for manufacturing the particles according to the present invention may be performed in a batch process, a multi-batch process, a [semi-batch process, or a continuous process. & The suitable reaction temperature is between 25 and 120 ° C. 15 i. Batch emulsion polymerization: Batch emulsion polymerization can be performed in many ways. For example, if a water-soluble starter is used, an emulsion can be formed from the monomer mixture, the water phase and a surfactant, and heated to the polymerization temperature required for the emulsion. The water-soluble starter and redox zibu were all added in the early stage of the polymerization process. Alternatively, the monomer may be added to an aqueous surfactant solution one time at the reaction temperature, followed by the (etc.) starting hydrazone. Right, an oil-soluble starter is used, which is usually dissolved in the beta monomer phase before emulsification. Then the '-emulsion can be formed from the monomer / starter mixture, the water phase and the surfactant, and heated to the aggregate of the emulsion f-13-200400201, the prison mouth and the' 俾So that polymerization occurs. Alternatively, the monomer / starting compound can be added to an aqueous surface active agent at night at a reaction temperature. The obtained emulsion can be left at the reaction temperature for several hours to several hours, until the desired degree of monomer conversion is reached. Additional starter batches can be added to complete the polymerization; the reaction can be heated after the Bebeti 70 is complete, so that a more complete polymerization can take place. 2. Multiple batches Another way to make these particles is to carry out the above polymerization, and then add a second batch of monomers, enough water to maintain the flow of the system to stir to emulsify, and add again. Initiators (if water-soluble initiators and redox agents are used), polymerize and repeat as needed. Fanyou uses an oil-soluble starter which can be dissolved in the monomer batch. In this way, a higher monomer / surfactant ratio can be obtained in the polymerization than in other possible ways. 15 Ronald's emulsion can be left at the reaction temperature for several minutes to several hours until the desired degree of monomer conversion is reached. Additional starter batches may be added to complete the polymerization reaction; the reaction may be heated after it is substantially complete, such that a more complete polymerization is achieved. 3. In a semi-batch of 20 a surfactant solution. There are many ways to proceed. For example, a separate logistics method is added

Another way to make these particles is to polymerize the monomers in a semi-batch mode, and continuously add the monomers and the initiator at the polymerization temperature to the same as batch polymerization. This mode can be water-soluble. The starting agent may be added separately from the monomer stream, and the oil-soluble starting agent may be added to -14-200400201 or dissolved in the monomer stream. The monomer stream can contain one or more monomers 'or each monomer can be added as a separate stream (either simultaneously' or sequentially, but each at a rate that varies over time). Aqueous components and surfactants can also be added during the polymerization process. The obtained emulsion can be left to stand at the reaction temperature for several minutes to several days, until the desired degree of monomer conversion is reached. Additional starter batches may be added to complete the polymerization reaction; the reaction may be heated after it is substantially complete, such that a more complete polymerization is achieved. 4 continuous 10 15 20

The polymerization can also be carried out in a continuous or "plunger flow" manner. The aqueous monomer emulsion and the initiator are mixed together at the desired polymerization temperature, and then injected to the appropriate Tube, and evacuate the tube after a period of time sufficient to complete the polymerization. Reagents, such as more monomers or initiators and analogs, and more surfactants or 疋 other aqueous components, can be used at various points along the tube if necessary

Force into the compound, and different areas of the tube can be heated or the crotch to different temperatures. The product emulsion can be continuously removed from the end of the tube. "After the particles are made by the above methods, the particles may be mixed with the emulsion by using an organic solvent or a solvent mixture which is at least partially soluble in water, and in the resulting aqueous phase-solvent mixture, The formed polymer is substantially insoluble. — The amount required for> cereals should be sufficient to substantially precipitate all the polymers formed from the hydrazide. Examples of such solvents include but It is not limited to endosyl ethyl ketone and methanol. This -15-200400201 granules can be used or heavy h-butyrolactone, tetrahydrofuran, the steps to separate these granules, these granules Freshly dispersed in a suitable organic solvent (eg, Glycogen, 135-dione or monopropylene glycol methyl ether acetate (DPMA) for subsequent use. Tertiary systems are also used to remove a solid mass No. 5 Surfactant residues. The particles can also be purified by various conventional methods, such as thorium-bed ion exchange resin before Shendian, (2) deionized water and selection

Solvents that the particles cannot dissolve are completely dissolved and washed, or the particles are allowed to settle, dispersed in an organic solvent, and the dispersion is passed through a silica gel soaked in a solvent. Or aluminum pillar. After Shendian, a drying step can be used, but it is important not to heat to a temperature that may cause the reaction groups remaining on the particles to react and cause an increase in clot and particle size.

Another specific example of this ignorance is a composition containing 15 crosslinked polymerized smoke particles, the composition is characterized in that the particles have a mean weight of less than 30 grams, and the particles show a The volume expansion coefficient of not more than 30, the particles are substantially free of metal ions, the particles have a polydispersity (Mw / Mn) of less than 3.0, and the characteristics of these particles are ... a Mark-Houwink A graph with an absolute 20 pair slope of less than 0.4 for the highest molecular weight range. Although these particles can be conveniently prepared by the above method, they can also be produced by conventionally using an ionic surfactant and / or an ionic starter. However, in this case these purification steps are required and / or will be more complicated. Preferably, the further characteristics of the particles are measured at -16-200400201 at · S by thermogravimetric analysis (from 25 to 600 C at a temperature increase rate of 10 ° C / min), at an inertia Thermal decomposition in the atmosphere shows a residue with less than 10 wt%, more preferably less than 5 wt%, and most preferably no more than 1% of the starting weight of the sample. 5 The weight average diameter of these particles is less than 30 nm, more preferably less than 25 nm 'and most preferably less than 20 nm. The weight-average diameter of the particles is preferably greater than 1.5 nm, and more preferably greater than 1.7 nm, and most preferably greater than 2.0 nm. The weight-average diameter can be determined by size-separation chromatography with a normal calibration of 10 and differential viscosity detection (SEC / DV). The SEC / DV test is performed as follows:-Good for the sample and the standard > Cereal, preferably polystyrene is selected. Tetrazine is a preferred solvent. The column for SEC separation contains pores, cross-linked PS particles, and the like, and is suitably adjusted to separate polystyrene and similar compounds based on the size (hydrodynamic volume) in solution. Traditional high pressure liquid chromatography (HPLC) equipment is used for solvent transfer and sample introduction. A differential refractive index detector is used to detect the concentration of the eluted sample. A differential viscosity meter is used to detect the specific viscosity of the eluent polymer solution. These detectors are commercially available, for example, a differential refractive index detector model 2410 from Waters and a differential viscosity meter model H502 from Viscotek. Because the concentration injected into the SEC system is small, the ratio of the special viscosity to the concentration at each SEC elution volume interval provides a reasonable estimate of the inherent viscosity of the polymer in the special volume interval. 200400201 This SEC / DV test makes it possible to obtain the following properties of the sample: Absolute molecular weight distribution (and number average, weight average, and z-average molecular weight); tightly packed and expanded (that is, in solvent) particle size distribution (and peak And weight average diameter); the Mark-Houwink plot (log [r |] vs. 10 gM, where [η] is solid and has viscosity, and M is molecular weight); the volume expansion coefficient in the test solvent, and the PS -Appearance molecular weight distribution (and molecular weight average and polydispersity). The general calibration curve is determined using a narrow molecular weight distribution polystyrene (pS) and, more preferably, a narrow molecular weight distribution polyoxyethylene (PEO) standard. 10 This curve is a plot of 10 g (h) * M) versus elution volume. The product of [η] * M is proportional to the hydrodynamic volume. Because the SEC type molecule is ideal based on the hydrodynamic volume, a single general calibration curve is obtained regardless of the polymer composition or structure. Therefore, after knowing the general calibration curve and intrinsic viscosity of each SEc elution volume interval, the absolute molecular weight of an unknown sample can be calculated for each elution volume. The weight-average diameter, DW, of the dried tightly packed particles is calculated as follows: # The absolute M value and polymer concentration data at each elution volume interval can be used to calculate the absolute molecular weight and distribution. The absolute molecular weight axis is converted into a particle size axis of 20, which is performed according to the following formula:

Dw (expressed in nm) = 2 * [(Mw) * (Li) * (density force) ... Among them, Mw is the absolute weight in g / mol. The average Yatsushiro system is the Avogari constant and the density is g / cm3 is a single mile ^ dry polymer-free presence, degree '1021 is a coefficient that converts cm3 to! ^ 3, and the -spherical appearance -18- 200400201 is assumed (ν = 4 / 3πι * 3). The coefficient 2 converts r (radius) to Dw (weight average diameter). The volume expansion coefficient (VSF) can also be conveniently measured by the SEC / DV test. In particular, the VSF system is defined as the expansion Divide the volume by the unexpanded volume. Because the SEC / DV experiment was performed in a good solvent, the inherent viscosity of the expansion was measured during the experiment and also in the expanded state. The inherent viscosity of the swelling can be predicted by the Einstein formula: ((η / λ 1) [η] {ηοη-swollen) = (1 / density) * Jjm = _ 2 · 5 Φ- ^ 〇Φ density 10 where the small system is The volume ratio of particles. VSF is calculated according to the following formula (multiply the density by the following formula, 俾 for generalization): VSF = expanded volume / unexpanded volume = [η] (expanded / [η] (Unexpanded) = [η] (Expanded) * (Density of Dry Polymer) /2.5 where [η] (Expanded) is the viscosity of the expanded solid I5 (solute) measured in the SEC / DV experiment Volume / mass). The density (g / cm3) of the dried Ps is used in the case of the preferred crosslinked polystyrene of the present invention. A method for determining the weight average diameter of the particles produced is by Standard SEC-laser light scattering (sec-llS) method. The standard SEC method is used, and the detection of the eluted sample is performed by a static laser light scattering detector 20 (measure the scattering intensity at three angles) The absolute weight average molecular weight can be directly determined in this way, for example, as described in the following references: Malcolm ρ Stevens, 2nd edmnd, Oxford University Press, 1990, pages 53 ^ 57; (2) Textbook of 200400201

Polymer Science, Fred W. Billmeyer, Jr., 3rd edition

Wiley-Inter science Publishers, 1984, pages 199-204; ⑺ Philip Wyatt, "Absolute Characterization 〇f Macromolecules," Analytica Chemica Acta, 272 5 140 (1993), and the average diameter of this tight weight, Dw, can be determined by The following formula is calculated:

Dw (expressed in nm) = (density where Mw is the absolute weight average molecular weight in g / mol, l is the Avogat constant, density is the density of the dry polymer in g / cm3, 10 1 〇21 is a coefficient that converts cm3 to nm3; and the density is the density of dry polystyrene, lg / cm3, and a spherical shape is assumed (V-4 / 3πτ). The coefficient 2 will be r (Radius) converted to £) w (weight average diameter). A third way to determine the z-average particle diameter is by standard methods of dynamic light scattering in a good solvent, such as tetrahydrofuran (THF), as described in 15 Ibid. From the mean expansion z_ average diameter obtained by this method, Dz good tincture, the tight z-average diameter]; ^, can be calculated by the following formula:

Dz (expressed in nm) = Dz good solubility * [VSF good solubility] -1/3 Wherein, the VSFu 测定 is determined by the differential viscosity meter in the good solvent 20 as described above. The z-average tightly packed particle diameter can be converted to a weight average tightly packed particle diameter, Dw by:

Dw (nm) -Dz (nm) * [Mw / Mz] 1/3 > where Mw and Mz are the absolute weight and the average molecular weight of -20-200400201 determined by the above-mentioned SEC DV t formula. ^ = The texture of the adult system is free of metal ions. The metal composition is determined by the standard method, inductively coupled galvanic mass spectrometry (ICP-MS) or neutron activity analysis (NAA). , 〆 ', have a polydispersity (Mw / Mn) of less than 3.0, preferably; more preferably less than 2.0. The polydispersity is derived from molecules that are relative to the linear polystyrene standard σ "mesh., Σσ /, has an absolute highest molecular weight from 4,000,000 to 578)! The polydispersity provides the composition in particle size The approximate value of the change. The characteristics of the particles such as 最, 亥, 亥, and 亥 are the characteristics of a mark_H⑽ ~. Figure 4 shows the slope of the absolute value of ㈣ · 4 for the highest molecular weight range. The absolute value of the slope is less than 0.3, and more preferably less than 0.2. The slope on the k Houwink graph represents the shape of the particles, a slope of 0.7 is characteristic of a substantially linear polymer, and a slope of 0 is Characteristics of a three-dimensional Newton 15 object (eg, a sphere). The slope of the Mark-Houwink diagram to be observed is from 25thwt% 2M (absolute molecular weight) to 75thwt% M. The particles may remain The vinyl group is on the inside and the surface of the particle. In addition, the particles may contain 20 functional groups of non-residual polyolefin on the inside and the surface. For example, the particles may contain hydroxyl, carboxylic acid ester, and IS , , Amidine, ester, or acetylene functional groups. These functional groups may exist as residual components of the following monomers: chloromethylstyrene, chlorostyrene, 2-hydroxyethyl acrylate, or f-based acrylate , Hydroxypropyl acrylate or methacrylate, 4-hydroxybutyl acrylate or γ-propyl-21-200400201 acid ester, phenylethynylstyrene, vinyl benzoic acid, acrylic acid, fluorenyl acrylic acid, Acrylamide, N-vinylamine, divinylbenzene, i, 3-diisopropylbenzene, etc., or may be removed by the reaction of the residual ethylenyl group with a functional compound Add, for example, the reaction of ethylene 5 in the particles with hydrogen under the catalyst, or with a reagent having at least one hydrogen-side bond 'followed by the oxidation of the resulting hydrogen-shed bond to generate a Alcohol functional groups. The inventors have found that the particles of the present invention are particularly useful as pore-forming agents (Porgen) when manufacturing porous membranes that are parent-linked. When used for this purpose, the The isoparticles and precursors are combined or mixed into a crosslinked matrix material. Examples of such matrix materials include benzocyclobutene resins (eg, Cyclotene ™ resins from Dow Chemical), polyarylene resins and polyarylene scale resins (eg, SiLKTM polyarylene resins from Dow Chemical) ), Silsesquioxane, etc. Preferably, the pore-forming agent is grafted to 15 " Hilquibe as a flooding agent. When the pseudo-bond unsaturated group remaining on the pore-forming agent can be obtained When reacting with reactive groups on these monomers, this can be accomplished by adding the pore-forming agent before the B-stage (partial polymerization). Alternatively, part of the B-stage can be formed by adding the pore Before the agent, and the pore former can be introduced by introducing the mixture sufficiently to cause the residual ethylenic 20-type unsaturated group on the pore former to react with the reactive group remaining on the b-stage reaction product. Condition while being grafted. The mixture is then applied to a substrate (preferably solvent coated, such as by spin coating by known methods). The matrix is cured and the pore former is removed by heating through its thermal decomposition temperature. Porous membranes such as these are used for manufacturing integrated circuits. The films are separated from each other and electrically isolate the conductive metal wires from each other. Embodiment C] Example 5 Reagents: styrene (S, 99%, Aldrich), divinylbenzene (DVB,

tech ·, 80%, Aldrich), 1,3-diisopropenylbenzene (DIB, 96%, Aldrich), 4-hydroxybutyl acrylate (Aidrich), h202 (30% aqueous, Fisher), t -Butyl hydroperoxide (tbhP, 70%, Alddch); ascorbic acid (Aldfich), 1-pentanol (Fisher), Aerosol-OTTM ionic surfactant 10 (AOT, 10% water, Sigma), ten Sodium dialkyl sulfate (SDS, 98%, Aldrich), 9-borabicyclo [3,3,1] nonane (9-BBN), dissolved in tetrahydrofuran to become 0.5M, Aldrich), Tergitol NPTM series nonyl Phenolethanol (Dow Chemical) and secondary alcohol ethanolic esters of the Tergitol 15-sTM (Dow Chemical) series were used as obtained. All polymerization reactions were carried out in ultrapure deionized water (UPD1-H20, passed through a Barnstead purifier, conductivity <10-17Ω-1) under nitrogen. Fisher Scientific HPLC grade solvents are used as obtained from beginning to end. Batch polymerization: Each emulsion is prepared by mixing the monomer mixture, the surfactant mixture and water with gentle stirring. The emulsified system was introduced into a temperature-controlled, N2-cleaned, appropriately sized reactor (glass or stainless steel) with uniform stirring (700-1000 rpm). The emulsion was stirred and purged with nitrogen for at least 20 minutes. 30% H202 or 70% TBHP and a suitable ascorbic acid solution (usually 2wt% water-23-200400201 solution) are quickly introduced at the set temperature (3 (TC, unless otherwise noted). Polymerization It is allowed to last for 1 hour, unless there is a special note in Table A. After 3-15 minutes of the initial reaction, an exotherm of 5 -17 ° C will typically be observed. 5 Separation of particles: method 1: Relative to a given volume of latex, an equal volume of methyl ethyl ketone (MEK) was added. The resulting suspension was centrifuged at 2000 rpm for 20 minutes (IEC Centra gp8r; i500G-force). The liquid system was decanted and the solid was resuspended, centrifuged, decanted (repeated twice) in 1 × UPDI water of the original volume, i.e. 10, and the solids were dried in accordance with The air stream is dried for about 70 hours. Separation of particles: Method 2: Relative to a given volume of latex, an equal volume of methyl ethyl group is added. The resulting suspension is separated as above ~. δHai and other liquid systems are decanted and these solids are connected It is mixed in upDi water and then added to acetone (equivalent volume). It is then filtered through 15 and a little volume of methanol or 1: 1 to water: acetone, then upm water ' Then it is methanol to wash the strips. The solids are dried in a dry air stream for about 70 hours. The particles are separated. Method 3: Relative to a given volume of latex, an equal volume of methyl ethyl _ System was added. The resulting suspension was as difficult as 20 above. The liquid system was decanted and the solid system was dissolved in a minimum amount of THF / Hocai 'and then slowly added the THF solution to -5 to 10 times to kill the crickets, and then wash the filter cake with methanol, and dry as above. -24- 200400201 Example 1 This example is shown in the present invention The representative batch polymerization in the method. The batch polymerization test is performed according to the general batch polymerization steps as described above, and the initial emulsion is prepared according to the formula in Table A, and has the characteristics of human particles. As presented in Table A. The particles are transparent, Method 2 comes From. A bit line through

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m cn oo oo i &gt; O rn rn rn 'O t—H rH rH rH r * H 8. inch 8 · inch 6 · (ν 6 · ε (ΝΙΤε (ΝΙΤ 388 · Ι 88 · Ι ε (Νinch ς.εοοΙSCK8I ος +? 5091091 ιον% 0Ι§0 /; Ιοο (Ν &lt; Ν, ε sas§ Ι.ς17 ς · &lt; Νς PQIabJO9r9 oo τι ζ / οο inch inch inch q cn I 3 Ι · ΙΙΙII F # fvp ^ h 澈 | inch Sb Γ0 Ϊ3ΓΙ cn mm oo &lt; N 〇9.SI 8s &lt; n In inch 9ε 9cn9ε S9.K inch ε.ΓΝΙε inch ε + 1W S τ τ τ τ. 嚤 «€雎 驷 wlr ^% Da 荽 荽 ο Bismuth 硪 ^^ 蚪 蚪 丨 w ^^ ir # 蜞 Hew * iHS-li. ^^ Bismuth makes bismuth ^^ 砘-衾Among the S4 sides W * 鹓 Tsukasa ^ 昶 ^ ^ ^ 屮 龌--© 11 鄱 * 鄱 03 &lt; polyester. * «€ ^ 驷)-^ aluminum love 0 蚪 bismuth 0 (yang_ # 蜞 贺 &gt; 0/3 Ann. Rose ^ Malaria and 驷 1 1!-Anger 龚 Gong ^ ^ $ -0 铼 铼 埏 埏 埏 寂 ^ ^ ^ ^ ^ ^ ^: ^ 街 ^ 丧 ^^ 刺 朱. ^ 吹 唉 回 忘 * ^ ifice 柃 ^ #: |: ^ 屮 ^ ^ H-ffi 衾 Chuojian he ^^ fir ^ ®w 相 Spider_ ^ 4 黢 W * 铋 藏 藏 放 放 ^^ 屮 屮 # Christine; 丨 ^, * 琳 ^ 彳 * |. ^^ but want to 驷 "-^ every like 0 蚪 bismuth, 0, ^^ 荦 &lt; 贺 &gt; 0038?: '° ———————— . «Let's make you evil *:» won 5 ^ + 200400 201 Example 2: This example shows a representative multi-batch polymerization in the method of the present invention. An emulsion formulation containing the following was formulated as described in the general procedure at 30 ° C using 3.9 1111. Ding 31 ^ and 4.8 1111 2% ascorbic acid was polymerized for 5 hours (丨 "Sample): 52.5 g of TergitolTMNP-15, 160 g of UPDI H20, and 38.5 g of 90 / l0 (w / w ) Styrene / divinylbenzene monomer mixture. Then, an additional 75 mU of UPDI h20 and 40.0 g of monomer mixture were added, and the reaction was stirred for 丨 hours, and then at 30 ° C. A 10 reaction was initiated with 3.0 ml of TBHP and 5.0 ml of 2% ascorbic acid, and the reaction was stirred for 1 hour (2nd sample). Then, an additional 50 ml of UPDI HW and 40.0 g of monomer mixture were applied. The reaction was initiated by adding 3.0 ml of TBHP and 5.0 ml of 2% ascorbic acid at 30 ° C, and the reaction was stirred for 1 hour (3th sample). Next, an additional 50 ml of UPDI ϋ20 and 40.0 g of the monomer mixture were added to the mixture, and the reaction was initiated at 30 ° C with 3.0 ml of TBHP and 5.0 ml of 2% ascorbic acid, and The reaction was stirred for 1 hour (4th sample). These particles are separated by the second method. Comparative Example 1: The polymerization was performed according to a general batch procedure using the reactants listed in Table A, and the particles were separated by Method 3. The Na + transmission through NAA was determined to be 27 + Λ1. Example 3: Ion exchange rhenium to remove metal: This example shows a purification method for particles prepared by the method of the present invention by cation exchange. The polymerization is performed according to the general batch steps.

Erya and the particles were not separated. The obtained latex system was divided into two halves, and the unprocessed whites were treated by 'WDI-WASH (UPDI H20) IWX 50_WXT strong acid (H + form) 7 W4 straight column Processor. The results are shown below.

Ppm Nano Untreated 23 ± 〇J ~ Treated N.D. @ 〇.i n.d. = Unable to measure under certain detection limits Example 4:

Ppm potassium 140 soil 7 N.D. @ 0.5 This example shows that 'while it is possible to purify particles made with an ionic surfactant, the remaining content of these metals is higher than particles made by the method 10 of the present invention. These purified particles may still meet the various limitations of the composition of the present invention. The following materials were mixed in a flask by stirring at room temperature: styrene (15 · 6 g), diethylbenzene (80%; 0.83 g), dodecyl sulfuric acid · sodium (45.1 g), 1-pentanol (16.1 g) '4-hydroxybutyl acrylate (0177 g), 15 &amp; UPDI water (423 g). The mixture was stirred until the eyes saw it as clear. The mixture was purged with nitrogen for 20 minutes and heated to 30C under nitrogen. Hydrogen peroxide (30% aqueous; .23 mL) and a 20/0 ascorbic acid aqueous solution were added. The polymerization lasted 60 minutes. This solid was isolated by Method 1. SEC Dv analysis indicated that the particle's straight 20-diameter system was 14.4 nm, and the volume expansion coefficient was 3.0. Purification: ι · 5 g of the obtained polymer was dissolved in 15 mL of CH2C12, and analyzed by chromatography on a silica gel-28- 200400201 (70-230 sieve), eluted with CHAl2, and the solvent was evaporated. After that, 1.39 g was obtained. The metal content was measured by ICP / MS and is recorded in Table B. Example 5: 5 Semi-batch polymerization: Dingliu 1101 ^ 154-15 surfactant (52.8§) and water (211.2 g) were added to a nitrogen-covered reactor, stirred and Purge with nitrogen for 30 minutes and heat to the set temperature (30 ° C). One consists of styrene (45.0 g), and divinylbenzene-80 (3.0 g), 1,3-diisopropenylbenzene (9.0 g), and 4- (1-butylphenylene) diene (3.0 g ) A single 10-body mixture, and two starter streams, a 30wt% hydrogen peroxide (9.0g) and a 2.0wt% aqueous ascorbic acid (3.0 §) were continuously added over 90 minutes 4 miles . The remote monomer mixture was added at a rate of 43.9 ml / hr, while H202 was 6.0 ml / hr 'and the ascorbic acid solution was 2.0 mi / hr. The reaction was allowed to proceed for 5 minutes after the additions were completed. The weight-average diameter determined by the sec DV method is 15.4 nm, and the volume expansion coefficient is 21 (the SEC DV result is obtained by using a column calibrated with polystyrene and polyethylene oxide) to obtain φ. And the ps-related polydispersity is 13 °. The tight z-weight average diameter calculated from the absolute weight average molecular weight determined by the sec_lls method is 16.6 nm. The particles were separated by Method 2. The gold 20 content is recorded in Table B. in·. The residue after heat treatment under nitrogen was 0.37 wt% as determined by TGA analysis. The Mark-H_ink diagram and the molecular weight distribution diagram are shown in FIG. 1. In Figure 1, the y-axis system of the molecular weight distribution graph is the differential of weight ratio relative to logM (dw / d10 gM), and the χ-axis system is the molecular weight (M) of -29-200400201 plotted on a log scale. . For the Mark-Houwink diagram, the y-axis is the intrinsic viscosity of the unit plotted in logarithmic scales per gram (relative to M also plotted in logarithmic units). The intrinsic viscosity value (labeled IV) is represented by a square, and the dw / dlogM value is represented by a smooth black line. 5 Table B-Metal content (ppb)

Example 2 Comparative Example 1 3 4 5 Element name (A1) 110 320 300 Magnesium (Mg) 氺 240 氺 Calcium (Ca) 510 1 350 430 Copper (Cu) 氺 660 110 Iron (Fe) 170 340 280 Potassium (K) 氺ND @ 500 PPb1 480 Samarium sodium (Na) 290 270001 ND @ 100 ppb1 100 220 Zinc (Zn) * 870 Chromium (Cr) * * * Zirconium (Zr) 氺 * 氺 Total 1080 Nd nd 4360 1340 * = not Detected, or above the LOQ, is usually 100 ppb. Other undetected or higher than this LOQ are: Ba, Be, Bi, Cd, Cs, Co, Ga, In, Pb, Li, Mn, Mo, Ni, Rb, Ag, Sr, Th , Sn, Ti, and V. 1. NAA analysis only Na and / or K. Example 6: This example shows the preparation of a porous membrane using the particles of Example 5 as a pore former. A round bottom flask equipped with a side-arm gas input valve was charged with 3.00 g of a monomer having the following chemical formula:

-30 200400201, 1.28 g of the granules described in Example 5 above, 80 c of yttrium-butyrolactone solvent, and a Teflon stir bar. After the reaction flask was sealed with a silicone rubber cover, the mixture was degassed by repeatedly venting and cleaning with dry, oxygen-free nitrogen. It was then placed in an oil bath of about 50 ° C with stirring, and the temperature of the oil bath was then raised to and maintained at 200-205T: for a period of 5 hours. At the completion of the reaction, the reaction mixture was cooled by being removed from the heated oil bath from 50 ° C, and cyclohexanone of 12.6 was added to rhenium to dilute the reaction product to a total solids content of 15%. The final mixture was filtered using a 0.45 μm Nailon filter membrane, and a part of the mixture was sprayed onto a silicon crystal circle in a clean space environment. The wafer was placed on a heating plate for 2 knives and 4 under a 15 ° C, nitrogen atmosphere to remove the solvents, and then cooled to room temperature. The coated wafer was then It was placed in an oven and heated under a nitrogen atmosphere at a heating rate of 7 it / min to 43 ° t, and was left to stand at this temperature for 15 to 40 seconds. When cooled to room temperature, the The obtained cross-linked porous dielectric film was identified by measuring its refractive index, light scattering properties, and obtaining a tunneling electron microscope (TEM) image to help determine the size of the pores. Compared to non-porous Refractive index values of polymer films of 6.633, and a refractive index value of 1 4691 were obtained. Observation of sample films using TEM showed a pore of about 7 3 2 nm / range of the same size (with an average of about 13 nm) Pore size). Example 7: Boronization of evaporated nano-sized particles This example shows a method for obtaining nano-sized particles with an optional functional group (hydroxyl in this example). Similar to the example The particle of 丨, 丨 g is related to -31-200400201

10 ml of THF and 9-borabicyclononane (9-BBN) in THF (0.5M, 7 ml) were mixed with each other. The reaction mixture was heated to reflux and stirred at this temperature for 1 hour. After cooling to 30 ° C, NaOH (3M, 5 ml) was added. Finally, the mixture was quenched with 1.5 ml of 30% 5 hydrogen peroxide and extracted with dichloromethane. After volatilizing the solvent, the cross-linked polystyrene particle mixture was precipitated into methanol to obtain hydroxyl-functional cross-linked polystyrene particles. The determination of the hydroxyl group is obtained by titration of tosylsulfonyl isocyanate dissolved in tetrahydrofuran. As is known in the art, the result is that each crosslinked styrene component has 28 OH groups, and the IS spectrum Showing an OH vibration at 3590cm_1

Moving belt. Using the same method, a crosslinked polystyrene particle prepared using divinylbenzene as a crosslinking agent instead of 1,3-diisopropenylbenzene is converted into a hydroxy-functional particle. In this example based on Raman spectroscopy (disclosed in Sundell, et al. Polym. Prepr. (Am. Chem. Soc. Div. 15 Polym. Chem.) 1993, 34, 546), the relative vinyl group The content is reduced to 0.136 to 0.074. Example 8 8 g of fluorenyl acrylate, 8 g of fluorenyl methacrylate, and 4 g of propylene methyl methacrylate were treated with activated basic alumina (50-200 mm) 20, respectively, to remove the resistance The chemical agent is then mixed. Tergitol NP30 (Ethanolated Surfactant S surfactant) (70.29 g of 70% activated) and 6.87 g of Igcpal CO-660 from Rhodia Company, ethanolized nonpant surfactant was dissolved in 200 ml of The deionized water is introduced into a stirred tubular reactor. The reactor was then accompanied by a stirrer at a speed of 200 rpm -32- 200400201, and then kept green with nitrogen for 20 minutes. A 10% hydrogen peroxide / fen solution and 10 ml of a 1% ascorbic acid solution were successively introduced into the reactor. The following mixture was injected into the reactor via an injection piston: 16.9 ml of monomer (injected at a rate of 4 mi / hour); 10 mi of 10% hydrogen peroxide solution (2 · 0 ml / hour) and 10 ml of a 1% ascorbic acid solution (2.0 such as / day). The reactor was stirred at 2000 rpm and cleaned with nitrogen at 20 ml / min, and the temperature was maintained at 24 ° F. Photon correction spectra were used to determine the number and volume average particle size of the products produced. Number The average particle size is 16 "nm, and the volume average particle size is 216 10 nm. An equal volume of methanol is added to the composition above, and the sinking system is at 5. Centrifuge at 2,000 rpm for 30 minutes. The suspension was decanted and the solid was suspended again at 100 ml of propylene. The suspension was precipitated by adding deionized water at 20 ° C, centrifuging and decanting for 15 minutes. The solids were dried overnight. The pore membrane was prepared according to the procedure described in Example 6 with the particles of this example. [Brief Description of the Drawings] Figure 1 is a molecular radon distribution diagram of a sample of one of the representative particles of the present invention and a Mark-Houwink diagram (intrinsic viscosity versus molecular weight in log units). [Representative symbol table for main elements of the diagram] -33-

Claims (1)

200400201 Scope of patent application: 1. A method for preparing a composition, comprising the following steps: combining at least one non-ionic surfactant and at least one aqueous phase component, and adding at least one to perform a radical polymerization reaction Monomer, adding a radical starter consisting essentially of an atom selected from the group consisting of 5 carbon, hydrogen, oxygen, and nitrogen atoms, and Heating 俾 to produce polymerized particles having a weight average diameter of less than 30 nm, wherein in all mixing, adding, and heating steps, the composition is substantially free of ionic surfactants and substantially free of There are any types of initiators other than carbon, hydrogen, nitrogen, and oxygen, and the addition and heating steps of 10 can occur in any order. 2. The method of claim 1 further comprises the step of precipitating the polymerized particles. 3. The method according to item 1 of the patent application scope, further comprising a step of purifying the composition after the polymerization reaction to remove the ionic species. 15 4. The method of claim 1 in the scope of patent application, wherein the radical initiator is substantially The upper system is composed of atoms selected from carbon, hydrogen, and oxygen, and the composition does not substantially contain a starter containing any atom other than carbon, hydrogen, oxygen, and nitrogen. 5. The method of claim 1 in which the monomer is essentially composed of atoms selected from carbon, hydrogen, oxygen, and nitrogen. 6. The method according to item 1 of the patent application, wherein the single system is a compound having one ethylenically unsaturated carbon-carbon bond capable of undergoing radical polymerization, and one having two capable of undergoing radical polymerization A second precursor of an ethylenically unsaturated carbon-carbon bond of the reaction was also added. 34 200400201 7. The method according to item 1 of the patent application, wherein the weight-average diameter is less than 20 nm. 0. The method according to item 1 of the patent application, wherein the aqueous phase component, the nonionic surfactant, and The monomers are combined to form an emulsion, the emulsion is heated to a temperature in the range of 25 to 90 ° C, and the initiator is added to the heated emulsion. 9. If the method according to item 8 of the scope of patent application, wherein after the initial reaction, a second batch of monomers and sufficient water-containing components for maintaining fluidity in the system are added, and the composition is stirred. To form a second emulsion, and 10 additional starters were added to generate additional particles. 10. The method of claim 1 in which the water phase component and the non-ionic surfactant are combined and heated to a temperature in the range of 25 to 90 ° c, and the monomer and the initiator Added continuously. 11. The method according to item 1 of the patent application range, wherein the non-ionic surface active agent 15 is selected from the group consisting of: polyoxyethylated alkylphenols; polyoxyethylated linear alcohols; poly Polyoxyethylene secondary alcohols; Polyoxyethylene polypropylene glycols; Polyoxyethylene thiols; Long-chain carboxylic acid esters; Glycerol and polyglycerol esters composed of natural fatty acids; Propylene glycol, sorbitol, and polyoxyethylated sorbitol Esters; polyethylene glycol esters and polyoxyethylated fatty acids; alkanolamine condensates; alkanolamines; alkyl diethylene 20 alcoholamines, 1: 1 alkanolamine-fatty acid condensates; 2: 1 alkanolamines -Fatty acid condensates; tertiary alkyne-type diols; polyoxyethylated silicones; η-alkylpyrrolidone; polyoxyethylated 1,2-alkanediols and 1,2-arylalkanediols; and Alkyl glycans ★ Shigan 0 12. The method according to item 1 of the patent application range, wherein the initiator is selected from: 35 200400201 2,2'-azobis (2-methylamidinopropane) dihydrogen Chloride, H202 / ascorbic acid, L-butyl hydroperoxide / ascorbic acid, dibutyl hydroperoxide, ~ butylperoxybenzoate or 2,2'-azoisobutyronitrile. 13. A composition comprising polymerized particles prepared by a method according to any one of claims 1 to 12. 5 14. A composition comprising cross-linked polymerized hydrocarbon particles, the composition is characterized in that the particles have a weight average diameter of less than 30 nm, and the particles exhibit a volume expansion coefficient of not more than 3.0, The particles are substantially free of metal ions; and the particles have a polydispersity 10 (polystyrene relative Mw / Mn) of less than 3.0. 15. For the composition in the scope of claim 14, wherein the particles are characterized by a Mark-Houwink diagram, the diagram has an absolute value of less than 0.4 for the highest molecular weight range. 16. The composition according to item 14 of the patent application, wherein the weight average diameter is 15 and less than 20 nm. 17. The composition according to item 14 of the application, wherein the hydrocarbon particles are a reaction product composed of a styrene monomer and at least one monomer having two ethylenically unsaturated groups. 18. The composition according to item 14 of the scope of patent application, characterized in that it has any metal ion contamination below 20 2 ppm. 19. The composition according to item 14 of the patent application, characterized by a total metal ion content of less than 10 ppm. 20. If the composition of the scope of application for patent No. 14 or 15 is substantially composed of cross-linked polymerized hydrocarbon particles, further features of the composition 36 200400201 lies in that a sample of the composition is at 1 (After thermogravimetric analysis from 25 to 600 ° C at TC / minute, the weight of the decomposed residue is less than 10% of the original weight of the sample. 21. If the composition of the scope of patent application item 13 or 14 , Which further comprises particles dispersed in a curable matrix precursor. 22. The composition of claim 21, wherein the curable matrix precursor is selected from the group consisting of Group: polyarylene, polyarylene ether, resin based on benzocyclobutene and resin based on silsesquioxane, and their monomeric or oligomeric precursors. 10 23. If applied The composition of the scope of patents No. 21 or 22, further comprising a solvent. 24. A method for manufacturing a crosslinked porous membrane, comprising the following steps: by applying the composition of the scope of patent No. 23 Apply to a substrate to make a coating A composition, curing a matrix precursor to form a cross-linked matrix polymer 15 and heating to a temperature higher than the thermal decomposition temperature of the particles to form holes in the film. The method according to item 24, wherein the substrate comprises a transistor. 26. The composition according to item 13 or 14 of the scope of application for a patent, wherein the particles are composed of an acrylate or fluorenyl acrylate functional monomer Reaction 20 is a reaction product composed of a mixture. 27. The composition according to item 21 of the patent application, wherein the particles are grafted to the precursor of the matrix. 28. A thin film including the application patent No. 21 Item composition 37.